CN102892582A - Laminated polyester film - Google Patents

Laminated polyester film Download PDF

Info

Publication number
CN102892582A
CN102892582A CN2011800237789A CN201180023778A CN102892582A CN 102892582 A CN102892582 A CN 102892582A CN 2011800237789 A CN2011800237789 A CN 2011800237789A CN 201180023778 A CN201180023778 A CN 201180023778A CN 102892582 A CN102892582 A CN 102892582A
Authority
CN
China
Prior art keywords
polyester film
coating layer
film
coating
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2011800237789A
Other languages
Chinese (zh)
Inventor
川崎泰史
藤田真人
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Plastics Inc
Original Assignee
Mitsubishi Plastics Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Plastics Inc filed Critical Mitsubishi Plastics Inc
Publication of CN102892582A publication Critical patent/CN102892582A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0273—Diffusing elements; Afocal elements characterized by the use
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/04—Prisms
    • G02B5/045—Prism arrays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/244—All polymers belonging to those covered by group B32B27/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
    • G02B2207/121—Antistatic or EM shielding layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/31794—Of cross-linked polyester

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

Provided is a laminated polyester film that can be suitably used in applications that require good visibility and adhesion with respect to a hard coat layer; for example, liquid crystal display members including various optical films and molding films. The laminated polyester film comprises a coating layer formed on at least one surface of a polyester film from a coating liquid containing a polyester resin containing a naphthalene skeleton, a metal oxide and an aromatic isocyanate compound.

Description

Laminated polyester film
Technical field
The present invention relates to a kind of polyester film, such as the laminated polyester film that relates to liquid crystal display, plasma display device, organic electroluminescent etc. and need to alleviate the interference spot that the reflection by extraneous light causes.
Background technology
In recent years, polyester film is multiplex in various optical films or molding film, is used for touch panel, antireflection film, prismatic lens, light diffusing sheet, electromagnetic shielding film or the purposes such as in-mold transfer printing film, in-mold label film as the member of liquid crystal or plasma display etc.The basement membrane (base film) that is used for these members is required the excellent transparency, visibility.
For performances such as the Anti-curling that improves these films, anti-damage and case hardnesses, mostly carry out hard conating processing.In addition, as substrate, the normal operation transparency, the polyester film that mechanical property is excellent.In order to improve the adhesive force of polyester film and hard conating, easily bonding coating layer is set generally speaking as the intermediate layer.Therefore, if do not consider polyester film, easy bonding coating layer, this refractive index of 3 layers of hard conating, will produce interference spot.
If will there be the film of interference spot to be used for the displays such as touch panel, then can become the poor goods of visibility, become unworkable product.Therefore, require to take some countermeasures for interference spot.It is generally acknowledged the refractive index be used to the coating layer that alleviates interference spot, should be near the geometric average of refractive index of the refractive index of polyester film of base material and hard conating that near the refractive index that is adjusted to this value is comparatively desirable.Because the refractive index of polyester film is high, so generally speaking need to design the refractive index of coating layer higher.
Improve the example of interference spot as the refractive index that improves coating layer, can enumerate the method (patent documentation 1) of the refractive index that metal oxide that for example the combination refractive index is high in coating layer and polymer binder improve coating layer.In addition, as other example, also has the method with metallo-chelate and resin combination.In this case, because the unstability of the metallo-chelate in the aqueous solution, so by combination the stable inadequate situation of coating fluid is arranged, in the situation of producing for a long time, might cause the increase (patent documentation 2) of liquid changing operation.In order to improve interference spot with these methods, in order to suppress coating layer the interference spot that the varied in thickness because of coating layer causes is occured by dissolution with solvents, the solvent that uses when often needing to select to form on the coating layer surface functional layer such as hard conating.Therefore, requirement can be used such as the rapid-drying properties solvent that uses in order to improve productivity ratio, the levelling agent that uses in order to improve surface state, in order to improve the coating layer of deliquescent various solvents for the resin of surface functional layer etc. no problemly.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2004-54161 communique
Patent documentation 2: TOHKEMY 2005-97571 communique
Summary of the invention
Invent problem to be solved
The present invention is the invention of finishing in view of above-mentioned actual conditions, the problem of its solution be to provide interference spot that a kind of reflection that can alleviate because of extraneous light causes, with the laminated polyester film of the adhesive force excellence of the various function of surface films such as hard conating.
Be used for solving the method for problem
The present inventor have carried out concentrated research in view of above-mentioned actual conditions, found that if use the polyester film with ad hoc structure, just can easily address the above problem, thereby finish the present invention.
Namely, main points of the present invention are to provide a kind of laminated polyester film, it is characterized in that at least one mask of polyester film the coating layer that is formed by coating fluid being arranged, this coating fluid comprises: the mylar, metal oxide and the aromatic isocyanate compound that contain the naphthalene skeleton.
The effect of invention
According to laminated polyester film of the present invention, can provide a kind of interference spot that causes because of the reflection of extraneous light during with various function of surface layer laminate such as hard conatings few, with the film of the adhesive force excellence of various function of surface films, its industrial value is high.
The specific embodiment
Consisting of the polyester film of laminated polyester film of the present invention, both can be that single layer structure also can be sandwich construction, beyond 2 layers, 3-tier architecture, only otherwise exceed main points of the present invention, can also be 4 layers or its above multilayer, is not particularly limited.
The polyester that uses among the present invention both can be that the homopolymerization polyester also can be copolyester.In the situation about being consisted of by the homopolymerization polyester, preferably use aromatic binary carboxylic acid and the resulting polyester of aliphatic dihydroxy alcohol polycondensation.As aromatic binary carboxylic acid, can enumerate terephthalic acid (TPA), NDA etc., as aliphatic dihydroxy alcohol, can enumerate ethylene glycol, diglycol, 1,4-CHDM etc.As representational polyester, can enumerate PETG etc.On the other hand, dicarboxylic acids composition as copolyester, can enumerate: M-phthalic acid, phthalic acid, terephthalic acid (TPA), 2,6-naphthalenedicarboxylic acid, adipic acid, decanedioic acid, hydroxycarboxylic acid are (for example, P-hydroxybenzoic acid etc.) etc. one or more in, as glycol component, can enumerate in ethylene glycol, diglycol, propane diols, butanediol, 4-cyclohexanedimethanol, season pentanediol etc. one or more.
In addition, in order to improve the weatherability of film, prevent for the pigment of colour filter etc. deterioratedly, also can make and contain ultra-violet absorber in the polyester film.Ultra-violet absorber is the compound with ultraviolet radiation absorption function, just is not particularly limited so long as can bear the compound of the heat that polyester film manufacturing process applies.
As ultra-violet absorber, organic ultra-violet absorber and mineral-type ultra-violet absorber are arranged, but consider from the viewpoint of the transparency, preferred organic ultra-violet absorber.As ultra-violet absorber, be not particularly limited, but can enumerate such as cyclic imide esters of gallic acid, benzotriazole, benzophenone etc.Consider from the viewpoint of durability, more preferably cyclic imide esters of gallic acid, benzotriazole.In addition, ultra-violet absorber also can be also with more than 2 kinds.
In the polyester layer of film of the present invention, to give sliding and to prevent that damage in each operation from as main purpose, also can cooperate particle.The kind of the particle that cooperates, just be not particularly limited so long as can give the particle of sliding, as object lesson, can enumerate such as particles such as silica, calcium carbonate, magnesium carbonate, brium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminium oxide, titanium oxide, organic granulars.In addition, can also in polyester manufacturing process, make a part of metal oxide precipitation, the loose precipitate particles that obtain of differential such as catalyst.
Laminated polyester film of the present invention in order to be used for various optical films or decoration film, preferably improves the transparency or distinctiveness.In order to improve the transparency, distinctiveness, the content that preferably is coupled to the particle in the polyester film is few.Therefore, preferably making the top layer that only makes film contains the sandwich construction of particle or makes the design that does not contain particle in the polyester film.In polyester film, do not contain in the situation of design of particle, in order to improve the operability such as sliding of polyester film, preferably make the design that coating layer contains particle.
In addition, can add as required existing known antioxidant, antistatic additive, heat stabilizer, lubricant, dyestuff, pigment etc. in the polyester film of the present invention.
The thickness of polyester film of the present invention so long as just be not particularly limited as the film-formable scope of film, but is generally the scope of 10～300 μ m, is preferably the scope of 25～250 μ m.
The below describes particularly to the Production Example of polyester film of the present invention, but is not subjected to any restriction of following Production Example.That is, preferably use previous described polyester raw material, with the molten sheet that the chill roll cooling curing is extruded, obtain the not method of drawing sheet from die head.In this case, in order to improve the flatness of sheet, preferably improve the adhesive force of sheet and rotation drum cooler, preferably adopt static to apply attachment method and/or liquid spreading attachment method.Secondly, resulting not drawing sheet is stretched at biaxially oriented.In this case, at first, adopt the stretching-machine of roller or stenter mode that above-mentioned not drawing sheet is stretched in one direction.Draft temperature is generally 70～120 ℃, is preferably 80～110 ℃, and stretching ratio is generally 2.5～7 times, is preferably 3.0～6 times.Then, the edge stretches with the direction of the draw direction quadrature of phase I, and in this case, draft temperature is generally 70～170 ℃, and stretching ratio is generally 3.0～7 times, is preferably 3.5～6.Then, continue the temperature at 180～270 ℃, straining at lower or 30% heat-treating under lax with interior, obtain Biaxially oriented film.In above-mentioned stretching, also can adopt to carry out the method for the stretching of a direction more than 2 stages.In this case, the mode that preferably is respectively above-mentioned scope with final stretching ratio at both direction stretches.
In addition, in the present invention, about consisting of the polyester film manufacturing of laminated polyester film, can also adopt simultaneously biaxial stretch-formed method.Biaxial stretch-formed method is that above-mentioned not drawing sheet is carried out under the temperature controlled state at common 70～120 ℃, preferred 80～110 ℃ simultaneously, the method that stretches simultaneously and be orientated along operating direction and width, as stretching ratio, count 4～50 times by the area multiplying power, be preferably 7～35 times, more preferably 10～25 times.Then, continue the temperature at 170～250 ℃, straining at lower or 30% heat-treating under lax with interior, obtain the stretch orientation film.Biaxial stretch-formed device when adopting above-mentioned stretching mode can adopt spiral way, scalable manner, linear drive mode etc. to have known stretching mode now.
Then, the coating fluid that uses in forming the coating layer that consists of laminated polyester film of the present invention is described.About coating layer, can arrange by the online coating of in the stretching process of polyester film, the film surface being processed, also can be used in the off-line coating that is coated with on the film of the external temporary transient manufacturing of system, can also and use both.Owing to can be coated with simultaneously with masking, so can reach cheap requirement of making, from utilizing stretching ratio the varied in thickness this respect of coating layer is considered, preferably use online coating.
With regard to online coating, be not limited to following mode, for example in biaxial stretch-formed one by one, implement especially coating before the cross directional stretch after longitudinal stretching finishes and process.When on the polyester film coating layer being set by being coated on online, can being coated with simultaneously with masking, and can processing coating layer at high temperature, can make suitable film as polyester film.
Laminated polyester film of the present invention, its necessary condition be, at least one mask of polyester film the coating layer that is formed by coating fluid arranged, and this coating fluid comprises: the mylar, metal oxide and the aromatic isocyanate compound that contain the naphthalene skeleton.
The mylar that contains the naphthalene skeleton among the present invention mainly is the resin that uses for the adhesive force of the refractive index of regulating coating layer and the surface functional layers such as improvement and hard conating.
As the method that the naphthalene skeleton is imported mylar, for example, have at naphthalene nucleus to import as substituent hydroxyl more than 2 or 2 as diol component or multi-hydroxy composition, perhaps import the method that 2 or 2 above carboxylic acid groups become to assign to realize as dicarboxylic acids composition or polybasic carboxylic acid.Consider from the viewpoint of the stability of mylar, preferably import the carboxylic acid group at naphthalene nucleus, as sour composition.As the naphthalene skeleton that has imported the carboxylic acid group, its representational compound can be enumerated NDA, 1,5-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid etc.Wherein, NDA particularly preferably.
In addition, as the constituent of the mylar that contains the naphthalene skeleton, also may be used polybasic carboxylic acid routine described as follows and multi-hydroxy compound with naphthalene skeleton.Namely, as polybasic carboxylic acid, can use terephthalic acid (TPA), M-phthalic acid, phthalic acid, phthalic acid, 4,4 '-diphenyldicarboxylic acid, 1,4-bicyclohexane dicarboxylic acids, 2-sulfonic acid potassium terephthalate, 5-sulfonic acid M-phthalic acid sodium, adipic acid, azelaic acid, decanedioic acid, dodecanedicarboxylic acid, glutaric acid, butanedioic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalate anhydride, P-hydroxybenzoic acid, trimellitic acid one sylvite and their ester formative derivative etc., as the multi-hydroxy compound, can enumerate ethylene glycol, 1, the 2-propane diols, 1, ammediol, 1, ammediol, 1, the 4-butanediol, 1, the 6-hexylene glycol, the 2-methyl isophthalic acid, the 5-pentanediol, season pentanediol, Isosorbide-5-Nitrae-cyclohexanediol, terephthalyl alcohol, bisphenol-A-ethylene glycol addition product, diglycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxy butylidene glycol, dihydromethyl propionic acid, glycerine, trimethylolpropane, dihydroxymethyl ethylsulfonic acid sodium, dihydromethyl propionic acid potassium etc.
Metal oxide among the present invention mainly is the compound that uses for the refractive index of regulating coating layer.Particularly because the refractive index of the resin that uses in the coating layer is low, so the preferred metal oxide with high index of refraction that uses with regard to refractive index, preferably uses the metal oxide more than 1.7.As the object lesson of metal oxide, can enumerate, such as zirconia, titanium oxide, tin oxide, yittrium oxide, antimony oxide, indium oxide, zinc oxide, antimony tin, tin indium oxide etc. both can be with they independent uses, and also two or more kinds may be used.In these metal oxides, more preferably adopt zirconia or titanium oxide, particularly consider from the viewpoint of weatherability, more preferably adopt zirconia.
Metal oxide, because using form different, the stability of adhesive force or coating fluid has the worry of decline, therefore, preferably the state with particle uses, in addition, consider that from the stability viewpoint of the transparency and coating fluid its average grain diameter is preferably the scope of 0.001～0.1 μ m, wherein, because the metal oxide that particle diameter is little can more easily carry out the adjusting of the refractive index of coating layer under the state that keeps the transparency, so preferred.But as described later, when using for the purpose that will give the operability such as sliding, also can marginally use average grain diameter in the scope of the harmless transparency is the particle of the scope of 0.1～1.0 μ m.
Aromatic isocyanate compound among the present invention mainly is in order to improve the adhesive force with the surface functional layer such as hard conating, and then uses for the durability that makes coating layer become firmly, improve the various solvents that use when forming surface functional layer.In addition, in the present invention, the adjusting outbalance of refractive index, therefore, the use refractive index can be than the aromatic isocyanate compound of aliphatic or alicyclic isocyanate compound design De Genggao.
So-called aromatic isocyanate compound refers to the isocyanate derivates of aromatic isocyanate or closure aromatic isocyanate representative and the compound that the result was generated that their NCO reacts when coating layer forms.As aromatic isocyanate, can enumerate, such as benzal vulcabond, xyxylene vulcabond, methylenediphenyl diisocyanates, phenylene diisocyanate, naphthalene diisocyanate etc., wherein, consider from the viewpoint of adhesive force, particularly preferably the benzal vulcabond.
When under the state of blocked isocyanate, using, as its sealer, can enumerate, bisulfite salt for example, phenol, cresols, the phenolic compounds such as ethyl-phenol, propylene glycol monomethyl ether, ethylene glycol, benzylalcohol, methyl alcohol, the alcohol compounds such as ethanol, dimethyl malenate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone,2,4-pentanedione isoreactivity methylene compounds, butanethiol, the sulfur alcohol compounds such as lauryl mercaptan, epsilon-caprolactams, the lactam analog compounds such as δ-valerolactam, diphenyl aniline, aniline, the aminated compounds such as aziridine, antifebrin, the sour amide compound of acetic acid acid amides, formaldehyde, acetaldoxime, acetoxime, methyl ethyl ketoxime, the oxime compounds such as cyclohexanone oxime, these sealers can also two or more kinds may be used separately.
In addition, the isocyanate derivates of above-mentioned aromatic isocyanate or closure aromatic isocyanate representative both can use separately, also can be used as mixture or bond use with various polymer.
In laminated polyester film of the present invention, in order to improve the coating surface state, interference spot when reducing the various surface functional layer such as coated face superimposed layer hard conating, to improve the transparency and adhesive force etc., also can and use various polymer.
As the object lesson of polymer, can enumerate the mylar that do not contain the naphthalene skeleton, acrylic resin, polyurethane resin, ethene polymers (polyvinyl alcohol, polyvinyl chloride, trichloroactic acid vinyl ester copolymers etc.), PAG, polyalkyleneimine, methylcellulose, hydroxylated cellulose, starch based etc.Among these polymer, consider from improving with the viewpoint of the adhesive force of the surface functional layer such as hard conating, preferably do not contain mylar, acrylic resin, the polyurethane resin of naphthalene skeleton.
And then, in the scope of main points of the present invention, also may be used aromatic isocyanate compound crosslinking agent in addition.As crosslinking agent, can use various known resins, can enumerate, such as aliphatic or alicyclic isocyanate compound, melamine compound, oxazoline compound, epoxide, carbodiimide compound etc.
In addition, the present invention is take the anchorage of improving coating layer, sliding as purpose, preferably contains the particle beyond the above-mentioned metal oxide in coating layer.Particularly in polyester film, do not contain under the design conditions of particle, in order to improve the operability such as sliding of film, be preferably designed for coating layer and contain the large particle of particle diameter than the particle of above-mentioned metal oxide.The average grain diameter of the particle that contains in the coating of using with this purpose is considered from the viewpoint of the transparency of film, is preferably the following scope of 1.0 μ m, and the scope of 0.05～0.7 μ m more preferably is particularly preferably the scope of 0.1～0.5 μ m.As the object lesson of particle, can enumerate silica, aluminium oxide, kaolin, calcium carbonate, organic granular etc., particularly consider from the viewpoint of dispersiveness, more preferably silica.
In the scope of main points of the present invention, equably with the coating fluid coating, also can add in right amount known anion surfactant or non-ionic surface active agent to the wetability of film in order to improve.In order more to improve the wetability to film, more preferably use fluorine class surfactant.
As fluorine class surfactant, refer to have the compound of the hydrocarbon chain that part or all of hydrogen atom replaced by fluorine atom.In addition, in the situation that makes water class coating fluid, fluorine class surfactant preferably has water-soluble or water dispersible to a certain degree, and for example, the hydrocarbon chain that can be set forth in the fluorine replacement has the compound of hydrophilic radical in addition.As hydrophilic radical, can enumerate, such as amine or the slaine of sulfonic acid, carboxylic acid, phosphoric acid etc., the halide salt of tertiary amine, hydroxyl or ether etc.
Fluorine class surfactant as anionic property, can enumerate perfluoroalkyl (C4～C12) lithium salts, sylvite, sodium salt and the ammonium salt of sulfonic acid, perfluoroalkyl (C7～C20) sylvite, sodium salt and the ammonium salt of carboxylic acid, perfluoroalkyl dicarboxylic acids sylvite, perfluoroalkyl phosphate etc.In addition, as the fluorine class surfactant of nonionic, can enumerate perfluoro octyl sulfonic acid diglycollic amide, N-propyl group-N-(2-ethoxy) perfluoro octyl sulfonic acid acid amides, perfluoroalkyl polyethylene glycol oxide ethanol, perfluoroalkyl alcoxylates etc.
And then in the scope of main points of the present invention, coating layer also can contain defoamer, tackifier, organic lubricant, antistatic additive, ultra-violet absorber, antioxidant, blowing agent, dyestuff, pigment etc. as required.
The ratio that contains the naphthalene nucleus in the mylar of naphthalene skeleton is preferably the scope of 5～80 % by weight, more preferably the scope of 10～60 % by weight.In addition, the ratio of the mylar that contains the naphthalene skeleton in the coating fluid is generally the scope of 5～90 % by weight, is preferably the scope of 10～85 % by weight, more preferably the scope of 15～80 % by weight.By in these scopes, using, just regulate easily the refractive index of coating layer, alleviate easily the interference spot after the surface functional layer such as hard conating forms.Wherein, the ratio of naphthalene nucleus, for example can enough suitable solvents or warm water coating layer is dissolved extraction, use the chromatography separation and Extraction, with NMR or IR structure is resolved, and then with thermal decomposition GC-MS(gaschromatographic mass spectrometric analysis) or optical analysis etc. resolve and try to achieve.
The ratio of the metal oxide in the coating fluid is generally the scope of 3～70 % by weight, is preferably the scope of 5～50 % by weight, and the scope of 5～40 % by weight more preferably is particularly preferably the scope of 6～30 % by weight.When quantity not sufficient 3 % by weight of metal oxide owing to can not improve fully the refractive index of coating layer, so sometimes can not alleviate interference spot, when surpassing 70 % by weight, sometimes the transparency of coating layer can variation or adhesive force descend.
The ratio of the aromatic isocyanate compound in the coating fluid is generally the scope of 1～50 % by weight, more preferably 5～40 % by weight, be more preferably the scope of 10～30 % by weight.When less than 1 % by weight, owing to descend with the adhesive force of the surface functional layer such as hard conating or coating layer dies down, thus humidity resistance might descend, when surpassing 50 % by weight, because the refractive index step-down of coating layer, sometimes bad because of the interference spot visibility of the surface functional layers such as hard conating after forming.
In the present invention, can contain in the coating layer for operability such as the slidings that improves film and the ratio of the particle that uses is preferably the scope of 0.1～5 % by weight, the scope of 0.3～3 % by weight more preferably is more preferably the scope of 0.4～2 % by weight.Under a few cases, need to improve the effect of the metal oxide particle that contains in the coating layer, or improve operability by containing particle in the film, on the other hand, in most cases the transparency of film can variation.
In polyester film of the present invention, also can coating layer also be set with the above-mentioned face that is provided with the face opposition side of coating layer.For example, form in the situation of the functional layers such as microlens layer, layers of prisms, anti-stick layer, light diffusion layer, hard conating, adhesive linkage, printed layers at the opposition side that forms the surface functional layer such as hard conating, can improve the adhesive force with this functional layer.Composition as form coating layer at the face of opposition side can use existing known material.For example, can enumerate the binder polymers such as mylar, acrylic resin, polyurethane resin; the crosslinking agents such as oxazoline compounds, epoxy compounds, melamine compounds, isocyanate ester compound etc., both can use separately these materials, also may be used multiple.In addition, coating layer (be identical coating layer on the polyester film two sides) also can contain above-mentioned mylar, metal oxide and the aromatic isocyanate compound that contains the naphthalene skeleton.
The analysis of the composition in the coating layer can adopt analyses such as TOF-SIMS, ESCA, fluorescent X-ray to implement.
When by online coating coating layer being set, preferably make laminated polyester film with following main points: above-mentioned a series of compounds are made the aqueous solution or aqueous dispersion, reach about 0.1～50 % by weight as the standard adjustment coating fluid, at this coating fluid of polyester film coating take solid component concentration.In addition, at the scope meat without detriment to main points of the present invention, for improving dispersiveness in water, improving the purpose of film forming, also can contain a small amount of organic solvent in the coating fluid.Organic solvent can only be a kind, also can suitably use more than 2 kinds.
About the laminated polyester film among the present invention, the thickness of set coating layer is generally the scope of 0.04～0.20 μ m on the polyester film, is preferably the scope of 0.07～0.15 μ m.When thickness departed from above-mentioned scope, because the impact of the interference spot after the stack surface functional layer, visibility is variation sometimes.
The method of coating layer is set among the present invention, can uses the existing known covering with paint modes such as reverse intaglio plate coating, directly intaglio plate coating, roller coat cloth, just mould coating, rod are coated with, curtain coating.
In the present invention, be not particularly limited about drying and condition of cure when polyester film forms coating layer, for example, adopting the off-line rubbing method to arrange in the situation of coating layer, usually with 80～200 ℃, 3～40 seconds, preferably heat-treat as standard and get final product take 100～180 ℃, 3～40 seconds.
In addition, adopting online rubbing method to arrange in the situation of coating layer, usually heat-treating as standard and get final product take 70～280 ℃, 3～200 seconds.
In addition, no matter off-line is coated with or online the coating, also heat treatment and ultraviolet ray can be shone the irradiation of isoreactivity energy line and usefulness as required.Polyester film to the formation laminated polyester film among the present invention also can be implemented the surface treatments such as sided corona treatment, Cement Composite Treated by Plasma in advance.
Coating layer among the present invention is the layer that has carried out adjustable refractive index for the generation that suppresses interference spot, and its refractive index designs near the geometrical mean of the surface functional layers such as the polyester film of base material and hard conating.The refractive index of coating layer and the reflectivity of coating layer have close relationship.With regard to absolute reflectance of the present invention, to draw transverse axis and represent that wavelength, the longitudinal axis represent the figure of reflectivity, the minimum of preferred reflectance is 1 in the scope of wavelength 400～800nm, this minimum is preferably more than 4.0%.In the scope of absolute reflectance of the present invention, if this minimum appears at identical wavelength, then minimizing reflectivity is high value when refractive index is high, is low value when refractive index is low.
Absolute reflectance among the present invention, preferably there is 1 minimum in the scope at wavelength 400～800nm, and more preferably there is 1 minimum in the scope at 500～700nm.In addition, this minimizing value is preferably 4.0～6.5% scope, more preferably 4.5～6.2% scope.When the minimum in the scope of wavelength 400～800nm is not 1, perhaps, when minimizing absolute reflectance departs from above-mentioned value, produce interference spot, the situation that the visibility of film descends after having surface functional layers such as forming hard conating.
Polyester film of the present invention generally arranges the surface functional layers such as hard conating at coating layer.Material as being used for hard conating is not particularly limited, but can enumerates, such as the solidfied material of simple function (methyl) acrylate, multifunctional (methyl) acrylate, tetraethoxysilane isoreactivity silicon compound etc.Among these materials, consider from the viewpoint of taking into account productivity ratio and hardness, be particularly preferably the polymerizing curable thing of the composition that contains ultra-violet solidified multifunctional (methyl) acrylate.
Be not particularly limited as the composition that contains ultra-violet solidified multifunctional (methyl) acrylate.For example, can use the composition that mixes more than one known ultra-violet solidified multifunctional (methyl) acrylate and form, as the commercially available composition of ultra-violet solidified hard coat material or in the purpose range of present embodiment, adding in addition the composition that other compositions form in addition to these.
Be not particularly limited as ultra-violet solidified multifunctional (methyl) acrylate, but can enumerate, dipentaerythritol six (methyl) acrylate for example, tetramethylol methane four (methyl) acrylate, tetramethylol methane three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, the polyfunctional alcohols' such as two (3-acryloxy-2-hydroxyl propoxyl group) hexanes of 1,6-(methyl) acrylic acid derivative or polyethylene glycol two (methyl) acrylate, also has polyurethane (methyl) acrylate etc.
Containing other compositions that comprise in the composition of ultra-violet solidified multifunctional (methyl) acrylate is not particularly limited.Can enumerate such as inorganic or organic particulate, polymerization initiator, polymerization inhibitor, antioxidant, antistatic additive, dispersant, surfactant, light stabilizer and levelling agent etc.In addition, making in its dry situation after the wet type rubbing method film forming, can add the solvent of any amount.
The formation method of hard conating can adopt the general wet type rubbing methods such as rolling method, firm mould rubbing method in the situation of using organic material.To formed hard conating, can implement as required heating or ultraviolet ray, the irradiation of electron ray isoreactivity energy line, be cured reaction.
Embodiment
Below, utilize embodiment that the present invention is described in further detail, but the present invention is only otherwise exceed its main points, just is not limited to following embodiment.In addition, determination method and the evaluation method used in the present invention are as follows.
(1) assay method of the intrinsic viscosity of polyester:
Oneself removes the polyester 1g of non-other component of polymer that mix and pigment to accurate weighing in polyester, and the mixed solvent 100ml that adds phenol/tetrachloroethanes=50/50 (weight ratio) makes its dissolving, measures in 30 ℃.
(2) assay method of average grain diameter:
Use TEM(Hitachi H-7650 processed, accelerating potential 100V) the observation coating layer, with the particle diameter mean value of 10 particles as average grain diameter.
(3) film thickness measuring method of coating layer:
Dyeed with RuO4 in the surface of coating layer, and be embedded in the epoxy resin., with RuO4 will with section that ultrathin sectioning make dye, with TEM(Hitachi H-7650 processed, accelerating potential 100V thereafter) mensuration coating layer section.
(4) evaluation method from the absolute reflectance of painting layer surface of polyester film:
Stick in advance black tape (the polyethylene tape VT-50 processed of NICHIBAN Co., Ltd.) at the mensuration back side of polyester film, use spectrophotometer (the Japanese light splitting ultraviolet-uisible spectrophotometer V-570 processed of Co., Ltd. and automatic absolute reflectance determinator AM-500N), with synchronous mode, 5 ° of incidence angles, the N polarisation, response Fast, data collection zone interval 1.0nm, bandwidth 10nm, sweep speed 1000m/min, to the absolute reflectance of coating aspect mensuration wave-length coverage 300～800nm, estimate its minimizing wavelength (end wave-wave long (bottom wavelength)) and reflectivity.
(5) assay method of interference spot:
Coating layer side at polyester film, coating dipentaerythritol acrylate 72 weight portions, 1,6-hexanediyl ester 18 weight portions, antimony pentoxide 10 weight portions, Photoepolymerizationinitiater initiater (trade name: IRGACURE184, Ciba system) the mixing masking liquid of 1 weight portion, MEK 200 weight portions, make dry film thickness reach 5 μ m, irradiation ultraviolet radiation makes its curing, forms hard conating.To resulting film, under 3 wavelength light territory type fluorescent lamps with the visual observations interference spot, confirm that with failing the film of interference spot is evaluated as ◎, the film that can confirm sparse scattered interference spot is evaluated as 〇, can confirm that film sparse and that be the interference spot of wire is evaluated as △, can confirm that the film of obvious interference spot is evaluated as *.
(6) evaluation method of adhesive force:
In order to carry out stricter adhesive force evaluation, use the material of having removed antimony pentoxide in the hard conating liquid that from above-mentioned (5) are estimated, uses to study.Namely, coating dipentaerythritol acrylate 80 weight portions, 1,6-hexanediyl ester 20 weight portions, Photoepolymerizationinitiater initiater (trade name: IRGACURE184, Ciba system) the mixing masking liquid of 5 weight portions, MEK 200 weight portions, make dry film thickness reach 5 μ m, irradiation ultraviolet radiation makes its curing, forms hard conating.To resulting film, after under 60 ℃, the environment of 90%RH, placing 100 hours, carry out 10 * 10 cross-cut (cross cut), attach the wide adhesive tape (NICHIBAN Co., Ltd. adhesive tape processed (registration mark) CT-18) of 18mm on it, release surface after observation is promptly peeled off with the peel angle of 180 degree, as to peel off area be that 3% of less than is evaluated as ◎, as be that 3% 10% of above less than is evaluated as 〇, as be that 10% 50% of above less than is evaluated as △, as be then be evaluated as more than 50% *.
The polyester that uses in embodiment and the comparative example is the polyester of preparing such as following operation.
The manufacture method of＜polyester (A) 〉
Take dimethyl terephthalate (DMT) 100 weight portions and ethylene glycol 60 weight portions as initiation material, four hydration magnesium acetate things, 0.09 weight portion is put into reactor as catalyst, to react the beginning Temperature Setting is 150 ℃, in distillation for removing methanol, make the reaction temperature rising, reach 230 ℃ after 3 hours.After 4 hours, make the ester exchange reaction physical end.After in this reactant mixture, adding 0.04 weight portion triethyl phosphate, add 0.04 weight portion antimony oxide, carry out polycondensation reaction in 4 hours.That is, temperature is heated up gradually from 230 ℃, reach 280 ℃.On the other hand, pressure reduces gradually from normal pressure, finally reaches 0.3mmHg.After the reaction beginning, the variation according to the stirring power of reactive tank stops reaction in the moment that is equivalent to intrinsic viscosity 0.63, adds at nitrogen and depresses, and polymer is discharged.The intrinsic viscosity of resulting polyester (A) is 0.63.
The manufacture method of＜polyester (B) 〉
In the manufacture method of polyester (A), after adding 0.04 weight portion triethyl phosphate, silica dioxide granule 0.2 weight portion, antimony oxide 0.04 weight portion in the ethylene glycol of being dispersed in that adds average grain diameter 1.6 μ m, stop polycondensation reaction in the moment that is equivalent to intrinsic viscosity 0.65, in addition, the same manufacture method of employing and polyester (A) obtains polyester (B).Resulting polyester (B) intrinsic viscosity is 0.65.
Consist of the compound example of coating layer, as follows.
(compound example)
The mylar that contains the naphthalene skeleton: (IA)
The aqueous dispersion of the mylar that obtains with following composition copolymerization
Monomer composition: (sour composition) NDA/5-sulfonic acid M-phthalic acid sodium // (diol component) ethylene glycol/diglycol=92/8//80/20 (mol%)
The mylar that contains the naphthalene skeleton: (IB)
Aqueous dispersion with the mylar of following composition copolymerization
Monomer composition: (sour composition) NDA/terephthalic acid (TPA)/5-sulfonic acid M-phthalic acid sodium // (diol component) ethylene glycol/diglycol=78/15/7//90/10 (mol%)
Metal oxide: (IIA) zirconia particles of average grain diameter 70nm
Metal oxide: (11B) zirconia particles of average grain diameter 15nm
Metal oxide: (IIC) titan oxide particles of average grain diameter 15nm
Aromatic isocyanate compound: (III)
In methyl ethyl ketone solvent, in adipic acid/M-phthalic acid // 1, the PEPA of 6-hexylene glycol=50/50//100 (mol%) (mean molecule quantity 1700) 100 weight portions, 1, in 4-butanediol 9 weight portions, trimethylolpropane 8 weight portions, after interpolation benzal vulcabond 80 weight portions react, add dihydromethyl propionic acid 12 weight portions, polyethylene glycol (mean molecule quantity 600) 16 weight portions, amine catalyst, react at 75 ℃.Then, add methyl ethyl ketoxime 16 weight portions at 55 ℃, generation contains closure isocyanates base polyurethane prepolymer.Mix again triethylamine 7.2 weight portions, water 450 weight portions, add triethylene tetramine 2.9 weight portions, make its reaction, remove methyl ethyl ketone solvent, obtain the closure aromatic isocyanate compound.
Mylar: (IV)
Aqueous dispersion with the mylar of following composition copolymerization
Monomer composition: (sour composition) terephthalic acid/isophthalic acid/5-sulfonic acid M-phthalic acid sodium // (diol component) ethylene glycol/BDO/diglycol=56/40/4//70/20/10 (mol%)
HMMM (V)
Particle: (VIA) silica dioxide granule of average grain diameter 0.45 μ m
Particle: (VIB) silica dioxide granule of average grain diameter 0.30 μ m
Particle: (VIC) silica dioxide granule of average grain diameter 0.16 μ m
Embodiment 1:
Polyester (A) is supplied with respectively extruder, after 285 ℃ of meltings, be extruded on the chill roll that is set as 40 ℃, make its cooling curing, obtain not drawing sheet.Then, adopt the roller speed discrepancy, longitudinally stretch after 3.4 times 85 ℃ of film temperatures, two-sided at this longitudinal stretching film, coating is shown in the coating fluid 1 of following table 1, imports stenter, along laterally stretching 4.0 times at 120 ℃, 225 ℃ heat-treat after, (dry after) is the polyester film of thickness 125 μ m of the coating layer of 0.09 μ m in transverse relaxation 2%, to obtain having thickness.
Measure the absolute reflectance of resulting polyester film, the result is, minimum is 580nm, and its reflectivity is 5.1%.Film behind the lamination hard conating does not have obvious interference spot, and adhesive force is also good.The characteristic of this film is shown in following table 2.
Embodiment 2～18:
In embodiment 1, except the smears composition being changed to the smears composition that is shown in table 1, operation is made similarly to Example 1, obtains polyester film.The polyester film of making is as shown in table 2, and high reflectivity, interference spot level are good in order to have, also good polyester film of adhesive force.
Embodiment 19:
The mixed material that polyester (A), (B) are mixed to get in 90%, 10% ratio respectively is as the raw material on outermost layer (top layer), with the raw material of polyester (A) as the intermediate layer, supply with respectively 2 extruders, each raw material is after 285 ℃ of meltings, be set as on 40 ℃ the chill roll, layer structure coextrusion with 2 kinds 3 layers (discharge rates of top layer/intermediate layer/top layer=1:18:1) makes its cooling curing, obtains not drawing sheet.Then, adopt the roller speed discrepancy, longitudinally stretch after 3.4 times 85 ℃ of film temperatures, two-sided at this longitudinal stretching film, coating is shown in the coating fluid 4 of following table 1, imports stenter, along laterally stretching 4.0 times at 120 ℃, 225 ℃ heat-treat after, (dry after) is the polyester film of the thickness 125 μ m of 0.09 μ m coating layer in transverse relaxation 2%, to obtain having thickness.
Measure the absolute reflectance of resulting polyester film, the result is, minimum is 580nm, and its reflectivity is 4.7%.Film behind the lamination hard conating does not have obvious interference spot, and adhesive force is also good.The characteristic of this film is shown in following table 2.
Embodiment 20:
In embodiment 19, except the smears composition being changed to the smears composition that is shown in table 1, operation is made similarly to Example 19, obtains polyester film.The polyester film of making is as shown in table 2, for having also also good polyester film of good, adhesive force of high reflectivity, interference spot level.
Comparative example 1～5:
In embodiment 1, except the smears composition being changed to the smears composition that is shown in table 1, operation is made similarly to Example 1, obtains polyester film.The laminated polyester film of making is estimated, and the result is as shown in table 2, can see the situation that can observe obvious interference spot, the situation of poor adhesive force.
［ table 1 ］
Figure BDA00002393540600161
[table 2 ］
Figure BDA00002393540600171
Wherein, in embodiment 5, adopt TOF-SIMS, the Bi32+ that shines as primary ions with the accelerating potential of 25kV measures, and the result can observe from the quasi-molecular ions of naphthalene nucleus with from the quasi-molecular ions of benzal vulcabond composition.In addition, utilize the fluorescent x-ray analysis, also can confirm to exist zr element.
Industrial utilizability
Film of the present invention can be applicable to pay attention to and the adhesive force of the surface functional layers such as hard conating and the purposes of visibility such as in as the various optical films of the members such as liquid crystal or plasma scope and molding film etc.

Claims (7)

1. laminated polyester film is characterized in that:
At least one mask at polyester film has the coating layer that is formed by coating fluid, and this coating fluid comprises mylar, metal oxide and the aromatic isocyanate compound that contains the naphthalene skeleton.
2. laminated polyester film as claimed in claim 1 is characterized in that:
The thickness of coating layer is 0.04～0.20 μ m.
3. laminated polyester film as claimed in claim 1 or 2 is characterized in that:
The ratio of the mylar that contains the naphthalene skeleton in the coating fluid is 5～90 % by weight, and the ratio of metal oxide is 3～70 % by weight, and the ratio of aromatic isocyanate compound is 1～50 % by weight.
4. such as each described laminated polyester film in the claim 1～3, it is characterized in that:
The average grain diameter of metal oxide is 0.001～0.1 μ m.
5. such as each described laminated polyester film in the claim 1～4, it is characterized in that:
Metal oxide is zirconia or titanium oxide.
6. such as each described laminated polyester film in the claim 1～5, it is characterized in that:
Aromatic isocyanate compound is the benzal diisocyanate cpd.
7. such as each described laminated polyester film in the claim 1～6, it is characterized in that:
The absolute reflectance of coating layer has 1 minimum in the scope of wavelength 400～800nm, and this minimizing absolute reflectance is more than 4.0%.
CN2011800237789A 2010-05-15 2011-04-07 Laminated polyester film Pending CN102892582A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2010-112711 2010-05-15
JP2010112711A JP5700953B2 (en) 2010-05-15 2010-05-15 Laminated polyester film
PCT/JP2011/058797 WO2011145405A1 (en) 2010-05-15 2011-04-07 Laminated polyester film

Publications (1)

Publication Number Publication Date
CN102892582A true CN102892582A (en) 2013-01-23

Family

ID=44991520

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011800237789A Pending CN102892582A (en) 2010-05-15 2011-04-07 Laminated polyester film

Country Status (6)

Country Link
US (1) US20130089730A1 (en)
EP (1) EP2572881A4 (en)
JP (1) JP5700953B2 (en)
KR (1) KR101768460B1 (en)
CN (1) CN102892582A (en)
WO (1) WO2011145405A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105705595A (en) * 2013-11-11 2016-06-22 日立化成株式会社 Binder for printing ink, laminate ink composition for soft packaging, and printed article

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5553627B2 (en) * 2010-02-07 2014-07-16 三菱樹脂株式会社 Laminated polyester film
JP5570289B2 (en) * 2010-04-29 2014-08-13 三菱樹脂株式会社 Laminated polyester film
JP2011245809A (en) * 2010-05-29 2011-12-08 Mitsubishi Plastics Inc Laminated polyester film
WO2011152172A1 (en) * 2010-05-29 2011-12-08 三菱樹脂株式会社 Multilayer polyester film
JP5489972B2 (en) * 2010-12-15 2014-05-14 三菱樹脂株式会社 Laminated polyester film
WO2012081438A1 (en) * 2010-12-15 2012-06-21 三菱樹脂株式会社 Layered polyester film
JP5489971B2 (en) * 2010-12-15 2014-05-14 三菱樹脂株式会社 Laminated polyester film
JP5655029B2 (en) * 2012-05-07 2015-01-14 三菱樹脂株式会社 Laminated polyester film
JP2014024896A (en) * 2012-07-25 2014-02-06 Mitsubishi Plastics Inc Laminated polyester film
JP2015021014A (en) * 2013-07-16 2015-02-02 三菱樹脂株式会社 Laminated polyester film
JP7091737B2 (en) * 2017-03-24 2022-06-28 東レ株式会社 Laminated film and its manufacturing method
CN116438074A (en) * 2020-11-24 2023-07-14 东洋纺株式会社 Easy-to-adhere polyester film

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5688454A (en) * 1979-12-21 1981-07-17 Toyobo Co Ltd Aqueous dispersion
US5217832A (en) * 1992-01-23 1993-06-08 The Walt Disney Company Permanent color transparencies on single substrates and methods for making the same
DE19720506A1 (en) * 1997-05-15 1998-11-19 Hoechst Diafoil Gmbh Transparent polyester film with high oxygen barrier, process for its production and its use
JP2000006345A (en) * 1998-06-19 2000-01-11 Mitsubishi Polyester Film Copp Composite polyethylene naphthalate film
JP2002071940A (en) * 2000-08-25 2002-03-12 Fuji Photo Film Co Ltd Optical filter, front plate and picture display device using the same
JP4052021B2 (en) * 2002-06-04 2008-02-27 帝人デュポンフィルム株式会社 Oriented polyester film and laminated film using the same
JP2004054161A (en) 2002-07-24 2004-02-19 Teijin Dupont Films Japan Ltd Optical easily adhesive polyester film
JP3632044B1 (en) 2003-08-21 2005-03-23 東洋紡績株式会社 Optically easy-adhesive polyester film and optical laminated polyester film
US7354653B2 (en) * 2003-12-18 2008-04-08 Eastman Chemical Company High clarity films with improved thermal properties
JP5162054B2 (en) * 2006-03-13 2013-03-13 三菱樹脂株式会社 Optical laminated polyester film
JP2008169277A (en) * 2007-01-10 2008-07-24 Teijin Dupont Films Japan Ltd Easily adhesive polyester film for optical use
JP2008183882A (en) * 2007-01-31 2008-08-14 Fujifilm Corp Laminate film for optical use and its production method and anti-reflection film and image display device
JP4661946B2 (en) * 2007-11-22 2011-03-30 東洋紡績株式会社 Optically easy-adhesive polyester film and optical laminated polyester film
JP5598892B2 (en) * 2008-04-21 2014-10-01 大日本塗料株式会社 Laminated transparent film
US8436084B2 (en) * 2008-07-16 2013-05-07 Kansai Paint Co., Ltd. Aqueous coating composition and method for forming multilayer coating film
JP5174591B2 (en) * 2008-09-08 2013-04-03 三菱樹脂株式会社 Laminated polyester film for light diffusion sheet
JP5174592B2 (en) * 2008-09-08 2013-04-03 三菱樹脂株式会社 Laminated polyester film for light diffusion sheet

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105705595A (en) * 2013-11-11 2016-06-22 日立化成株式会社 Binder for printing ink, laminate ink composition for soft packaging, and printed article
CN105705595B (en) * 2013-11-11 2018-07-31 日立化成株式会社 Adhesive for printing ink, flexible package laminating inks composition and printed article

Also Published As

Publication number Publication date
KR101768460B1 (en) 2017-08-16
EP2572881A1 (en) 2013-03-27
US20130089730A1 (en) 2013-04-11
JP5700953B2 (en) 2015-04-15
EP2572881A4 (en) 2014-01-15
JP2011240533A (en) 2011-12-01
KR20130085940A (en) 2013-07-30
WO2011145405A1 (en) 2011-11-24

Similar Documents

Publication Publication Date Title
CN102892582A (en) Laminated polyester film
CN102791486B (en) Laminated polyester film
CN102470655B (en) Multilayer polyester film
CN102762379B (en) Laminated polyester film
CN102905899A (en) Layered polyester film
CN102548762B (en) Laminated polyester film
CN102438831B (en) Optics readily bondable polyester film
CN102427943B (en) Laminated polyester film
CN102458850A (en) Laminated polyester film
CN102395469B (en) Laminated polyester film
CN102905898A (en) Layered polyester film
CN102171038A (en) Multilayer polyester film
CN103328212A (en) Layered polyester film and hardcoat film
CN102112309A (en) Laminated polyester film and antireflection film
CN103796831B (en) Coated film
CN103889720B (en) Polyester film
CN103228446A (en) Laminated polyester film
CN102470654A (en) Laminated polyester film
JP2011246663A (en) Laminated polyester film
CN105037772B (en) Coated film
CN103889722B (en) Coated film
CN103649188A (en) Coating film
CN103619588B (en) Coated film
TWI633010B (en) Laminated polyester film
CN103889721A (en) Coating film

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20130123